Preparation of polyhaloisoalkoxyalkanoic acids and derivatives thereof

ABSTRACT

Antimony pentahalides selected from the group SbC15, SbF5 and SbF3C12 catalyze the oxidation of polyhaloisoalkoxy-alkyl iodides with SO3 or oleum. The products of the reaction are the corresponding acid halides and pyrosulfuryl halides which may be converted to the free acids or acid derivatives. The acids, salts and esters thereof are surface active. The acids are further useful as stain repellent agents.

United States Patent Sweeney et al.

[ 1 *Oct. 24, 1972 [54] PREPARATION OF POLYHALOISOALKOXYALKANOIC ACIDSAND DERIVATIVES THEREOF [72] Inventors: Richard Francis Sweeney, Elma,N.Y.; Charles Cheng-Yu Yao, Long Valley, NJ.

[73] Assignee: Allied Chemical Corporation, New

York, NY.

The portion of the term of this patent subsequent to Feb. 3, 1987, hasbeen disclaimed.

221 Filed: Oct. 1,1969

21 Appl.No.: 862,953

[ Notice:

[52] US. Cl. ..260/544 F, 260/468 R, 260/484 R [51] Int. Cl ..C07e 51/58[5 8] Field of Search ..260/544 Y, 544 F [56] References Cited UNITEDSTATES PATENTS 3,493,6l I 2/ I 970 Sweeney ..260/544 3,102,139 8/1963Lawlor ..260/546 3,351,644 1 H1967 Hauptschein "260/408 2,511,072 6/1950McCann ..23/l74 OTHER PUBLICATIONS Lovelace et al., Aliphatic FlourineCompounds, (1958) Rheinhold pp. 221- 222.

Noller, Chemistry of Organic Compounds, 3rd ed. (1965) Saunders p. 161

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Richard D.Kelly Attorney-Jay P. Friedenson [5 7] ABSTRACT 30 Claims, N0 DrawingsPREPARATION OF POLYI-IALOISOALKOXYALKANOIC ACIDS AND DERIVATIVES THEREOFCROSS-REFERENCES TO RELATED APPLICATIONS AND PATENTS l. U. S. Pat. No.3,453,333 to Litt et al., entitled Fluorinated Ethers, issued July 1,1969.

2. Copending application of Litt et al., entitled Fluorinated Ethers,Ser. No. 513,574, filed Dec. 13, 1965.

3. Copending application of Anello et al., entitled Telomers and Processfor the Preparation Thereof, Ser. No. 633,359, filed Apr. 25, 1967.

4. Copending application of Anello et al., entitledPolyfluoroisoalkoxyalkyl Halides, Ser. No. 818,832, filed Apr. 23, 1969.

5. Copending application of Anello et al., entitled FluorocarbonCompounds, Ser. No. 721,117, filed Apr. 12, 1968.

6. Copending application of Anello et al., entitled Fluorocarbon Acidsand Derivatives, Ser. No. 72l,ll5,filedApr. 12,1968.

7. Copending application of Sweeney et al., entitled Preparation ofPerfluoroacyl Fluorides, Ser. No. 525,143, filed Feb. 4, 1966.

BACKGROUND OF THE INVENTION Copending applications of Anello et al.,Ser. Nos. 721,117 and 721,115, mentioned supra, cover novelplyhaloisoalkoxyalkanoic acids and derivatives thereof, useful assurface active agents, strain repellent agents and as intermediates forthe preparation of other surface active and stain repellent agents.

Certain polyhaloalkanoic acid fluorides have been prepared byoxidation-of polyhaloalkyl iodides with 80;, or oleum (U. S. Pat. No.3,102,139 and 3,351,744). The resulting acid fluorides may then beconverted to the free acids and various acid derivatives by conventionalmethods. Oxidation of perfluoroalkyl iodides to the corresponding acidfluorides, particularly in the absence of a catalyst, is notoriouslydifficult with very low conversions, if any, being obtained. When it wasattempted to apply these procedures to prepare the subject class ofether acids, it was found that the conversions of the correspondingether iodide starting materials to the acid products were exceedinglysmall.

Accordingly, the object of the present invention is to provide acatalyst for the reaction between polyhaloisoalkoxyalkyl iodides and80;, or oleum to enable higher conversions of the iodides to the acidicproducts to be obtained.

SUMMARY OF THE INVENTION It has been found that the reaction between theherein defined class of polyhaloisoalkoxyalkyl iodides and S0 or oleumto produce the corresponding acid fluorides, is catalyzed by an antimonypentahalide selected from the group consisting of SbCl SbF and SbF Cland mixtures thereof. As compared with noncatalyzed runs of thesereactions, the rate of reaction is substantially increased andsignificantly higher conversions of the iodide starting material to theacid products are obtainable. The obtainment of a substantially higherreaction rate is of further advantage since it permits the reaction tobe carried out effectively at atmospheric pressure and at relatively lowtemperatures. The novel catalytic process is of particular value for thesynthesis of the difficult to prepare perfluorinated acid species inaccordance with the invention.

The class of polyhaloisoalkoxyalkyl iodide starting materials which maybe used in accordance with the invention process is defined by thefollowing formula.

wherein R R are independently selected from the group consisting of F,Cl, alkyl and haloalkyl groups in which the halogen atoms are C1 or F,R, and R when taken together and with the carbon chain therebetween,form a cyclic structure, R is alkylene or haloalkylene in which thehalogen atoms are selected from C1 and F, Y, is selected from C1 and F,and Y is selected from H, F, C1 and perhaloalkyl groups in which thehalogen atoms are selected from F and C1.

The major direct acidic products of the subject reaction are thecorresponding acid fluorides of the formula:

wherein R -R and R are as defined above. Minor amounts of pyrosulfurylhalides are formed as byproducts.

DETAILED DESCRIPTION OF THE INVENTION AND OF THE PREFERRED EMBODIMENTSWith reference to formula (I) for the iodide starting materials usefulin accordance with the invention process, R R if alkyl or haloalkylgroups, may be straight chain or branched chain. There is no particularcriticality as to the number of carbon atoms in such groups. A preferredcarbon content for such groups is from one to nine carbon atoms andstill preferred is from one to two carbon atoms. R R., are preferably F,C1 or perhaloalkyl groups. Still preferably, any perhaloalkyl groups areperfluoroalkyl groups. When the R R groups contain chlorine substitutionor hydrogen substitution, it is preferred that enough fluorinesubstitution be provided so that the atomic ratio of fluorine tochlorine atoms to the hydrogen atoms or to the combined total of thechlorine and hydrogen atoms, is at least 1:1. In the most preferredembodiment R --R are all F.

There is no particular criticality for the carbon content of the R groupin formula (I). Preferably, the R group contains one to carbon atoms,still preferably from one to 40 carbon atoms, and most preferably fromone to 15 carbon atoms. When R contains chlorine substitution orhydrogen substitution, it is preferred that enough fluorine substitutionbe provided so that the atomic ratio of fluorine to chlorine atoms tohydrogen atoms, or to the combined total of the chlorine and hydrogenatoms, is at least 1:1. A preferred structure for the R group is (CF)m(Cl-l )n wherein m is an integer of from one to 40, preferably one to15, and n is or an integer of from one to 40, preferably one to 15. TheR group is still preferably a perhaloalkylene group and most preferablyis a perfiuoroalkylene group containing one to 15 carbon atoms. The Rgroup is saturated and may be straight chain or branched chain, cyclicchain or a combination thereof.

When Y is a perhaloalkyl group, Y preferably contains one to six carbonatoms, and still preferably from one to three carbon atoms.

The polyhaloisoalkoxyalkyl iodide starting materials are the telogen andtelomer products which are disclosed in U. S. Pat. 3,453,333 andcopending applications Ser. Nos. 513,574, 633,359 and 818,832, mentionedsupra. Polyhaloorganoalkyl iodide starting materials of formula (I) inwhich R contains a single carbon atom, are telogens which may beprepared by reacting an appropriate perhalogenated cyclic or acyclicketone with an ionizable fluoride salt, e.g., KF, to form a fluorinatedorganic salt and then reacting the organic salt with a halogen otherthan fluorine (e.g. iodine or bromine) and an appropriate olefin, suchas tetrafiuoroethylene, in the presence of an inert organic solvent, toform the desired telogen. The reaction between the perhalogenated ketonewith the ionizable fluoride salt proceeds readily at room temperatureand is best carried out under anhydrous conditions in the presence of aninert organic solvent such as acetonitrile or dimethyl formamide. Thereaction between the fluorinated organic salt with the olefin and ahalogen also proceeds readily at room temperature and may be conductedin the same solvent medium as the first mentioned reaction. Thesereactions are more fully described in U. S. Pat. 3,453,333 and copendingapplication Ser. No. 13,574, mentioned supra.

The longer chain polyhaloorganoalkyl iodide starting materials,possessing an even number of carbon atoms linking the oxygen and iodineatoms, are telomers which may be prepared by telomerizing the telogensdescribed above with a telomerizable unsaturated material comprising anolefin possessing only halogen and hydrogen substituents.

The telogens may first be telomerized to a desired molecular weight witha first olefin and then the resulting telomer product may optionally befurther telomerized to a higher molecular weight with an additionalolefin or olefins. Preferably, the olefin or olefins reacted with thetelogens are so chosen and the degree of telomerization is so adjustedthat the R moiety possesses a ratio of halo atoms to hydrogen atoms ofat least 1:1.

The telomerization reaction is carried out under free radicalconditions. The free radicals are preferably produced with thermalinitiation of the reaction and this is accomplished simply be heatingthe reactants to an elevated temperature. The elevated temperatureshould normally be between about 100 0. and 350 C., preferably betweenabout 150 C. 200 C. Alternative- 1y, conventional free radial generatingcatalysts may be employed to initiate the reaction. Although thereaction may be conducted at atmospheric pressure, superatmosphericpressures, for example, up to about 20,000 p.s.i.g. may be used withpressures between about 100 p.s.i.g and about 10,000 p.s.i.g. beingespecially preferred. The chain length of the resulting product isinfluenced by the reaction period which may 5 vary from about minutes toabout two weeks.

The ratio of telogen to olefin may vary from about 1:75 to as high as200:1, the preferred ratio for batchwise operation being about 1:1 to2:1 in the production of relatively low molecular weight telomers, i.e.,telomers containing up to about 6 or 7 monomer units per telomermolecule. On the other hand, in a constant pressure'reaction, i.e.,where a constant pressure of olefin is maintained above the liquid phasecomprising the telogen during the reaction, the molecular weight oftelomer product may be controlled by varying the pressure of the olefin.In general, the higher the pressure of the olefin, the higher themolecular weight of the telomer product.

The telomerization reaction inherently produces a mixture of telomers ofvarying chain lengths and corresponding varying molecular weights. Theaverage chain length and the spread of molecular weight produced by thetelomerization reaction may be controlled within limits as discussedabove by varying the reactant proportions, reaction time, reactiontemperature, reaction pressure and other reactionvariables. If desired,individual telomer products can be separated from mixtures thereof byconventional separatory techniques, for example, by fractionaldistillation, fractional crystallization using an inert solvent such asdiethyl ether, or the mixture of telomer products may be separated intofractions of narrower ranges of molecular weights having a desiredviscosity or other properties.

The telomerization reaction is described in more detail in copendingapplication Ser. No. 633,359, mentioned supra, and in correspondingBelgian Pat. No. 714,162.

Illustrative olefins suitable for telomerization include the following:CF =CF CF =CH CF =CClF, CF3=CFg, CH =CH CC]z=CH2,

CF: ("3F i EF and CF, F, F, Cz cz cH,=c c,H, Many more suitable olefinswill readily occur to one of ordinary skill in the art. The longer chainsol fiafirgafio alkyliodide start ing materials, possessing an oddnumber of carbon atoms linking the oxygen and iodine atoms, are telomerswhich may be prepared by the following procedure. A polyhaloorgano alkyliodide telogen as defined by formula l above, wherein the R group contains one carbon atom, is reacted with sulfur trioxide to form an acidhalide. This reaction is carried out at temperatures between about 50l75C. Preferably, an excess of S is used and sufficient pressure isemployed to maintain the reactants in liquid phase. The acid halide ishydrolyzed to the acid by refluxing in water. The resulting acid has asingle carbon atom linking the oxygen atom with the carboxy group. Thisacid can then be converted to the corresponding telogen iodidepossessing a single carbon atom linking the oxygen and iodine atoms bythe well known Hunsdiecker reaction which involves reacting the acidwith alkali-free silver oxide (Ag O) to form the silver salt, followedby reaction of the silver salt with powdered iodine to form the iodide.This telogen iodide can then be telomerized with one or more olefins toproduce telomer iodides having an odd number of carbon atoms linking theoxygen and iodine atoms. Illustrative procedures are shown as follows:s03

(CF;,) CFOCF CF l (CF CFOCF COF (CFQ CFOCF COF (CF CFOCF COOH cancrocrcoon i; (CF CFOCF COOAg (CF CFOCF COOAg (CF CFOCF l (CF CFOCF l(CF3)2CFOCF2(CF CF2) I CF2=CH2 (C Fa)2CFOC FAG FgC FZ)mI ployed, forexample, as low as about 0.02 mol of catalyst per mol of iodide startingmaterial reactant. in the interest of obtaining greater conversions ofstarting material within shorter reaction periods, larger quantities ofthe catalyst should be used. A satisfactory operating range of catalystconcentration to iodide starting material is between about 0.3 to 2.0mols of catalyst per mol of iodide starting material. A preferred molarratio of the antimony pentahalide catalyst to the iodide startingmaterial is from about 2:1 to 1:1 and still preferably from about 2:1 to1.5: 1. Use of catalyst concentration above 2011 does not deleteriouslyaffect the reaction but does not contribute significantly move to thereaction rate and is uneconomical. The catalyst may be added all atonce, in small portions or continuously over the reaction period. Forreasons of convenience it is preferred to add the entire amount ofcatalyst at the beginning of the reaction.

Although the stoichiometry of the reaction would seem to require one molof oxidizing agent per mol of perfluoroalkyl iodide starting material,it has been found that, for best results, a stoichiometric excess of theoxidizing agent relative to the amount of iodide starting material,should be employed. The ratio of o mic F0 0 F(C F20 Fnmwmo F1) .1

It should be noted that the above-noted telomerization reaction producestwo products (A) and (B). The (A) product is obtained in about a 95percent yield. The (B) product is obtained in about a percent yield. The(A) and (B) products can be separated by conventional procedures. Forexample, deydroiodinating the (A) and (B) product mixture with KOH at75l50 C. preferentially converts product (A) to the corresponding olefinwhich can then readily be separated from product (B) by distillation.

Other methods can readily be devised by those skilled in the art forpreparing polyhaloorganoalkyl iodide starting materials suitable for usein the invention process.

50;, if used as the oxidizing agent, may be added in any physical statebut is presently added in liquid form. Unstabilized liquid sulfurtrioxide may be used but technical grade, stabilized forms of liquidsulfur trioxide are convenient and are well suited for use.

The oleum reactant consists of H 80 and S0 For example, so-calledpercent oleum consists of 80 percent by weight H 80 and 20 percent byweight free S0 The H 80, component of the oleum will be understood asbeing 100 percent H 80 concentration. The term oleum as used herein isintended to refer to any mixtures of S0 and 100 percent H 80 There isnot upper limitation on the S0 strength of the oleum which may be usedaccording to the invention process since pure S0 may be used. If theacid halide product is desired in favor of the free acid, the S0concentration in the oleum mixture should be at least about 20 percentand preferably in the range of about 20 to 70 percent and, stillpreferably, from about to 50 percent. If the free acid is sought, suchcan be favored in the product mixture by maintaining the S0concentration of the oleum employed below about 20 percent.

The reaction between the iodide starting material and oxidizing agentwill proceed even when only trace amounts of the antimony pentahalidecatalyst are em- S0 either alone or dissolved in sulfuric acid to formthe oleum reactant, tothe iodide starting material, is accordinglypreferably maintained in the range of about l.l-20:l. Use of higherconcentrations of S0 does not deleteriously affect the reaction butwould not be economical. The preferred ratio of to the starting materialis in the range of about 3-15: 1

The reaction temperature is not critical and may vary over a wide rangesuch as from about zero up to the reflux temperature of the reactionmixture. For best results the reaction should be run at the refluxtemperature of the reaction mixture. This will depend largely on theproportions of the reactant present and upon the boiling point of theproduct. In the case of SO the reflux temperature will usually be atleast about 40 C. whereas with oleum the reflux temperature will usuallybe at least about C.

One of the, major advantagesof the invention process is that it can beefficiently run at atmospheric pressures, thus obviating the expense andinconvenience of operating high pressure equipment. If desired, however,superatmospheric or subatmospheric pressures may be employed. Elevatedpressures would tend to diminish reaction times.

Reaction time for complete conversion is normally between about 18-48hours. Substantial amounts of product will, however, ordinarily beformed after about one half hour of reaction. End point of reaction maybe determined by observing when the reflux temperature of the productmixture remains constant over a significant period of time.

The process is carried out by heating a mixture of the selected iodidestarting material, a selected antimony pentahalide catalyst, and eithersulfur trioxide or oleum, preferably to the reflux temperature of themixture. bower boiling products of the reaction which tend to distillfrom the mixture may be condensed in a cold trap. At the end of thereaction period the mixture is cooled to ambient temperature. Theorganic materials in the product mixture have limited solubility in theinorganic portion of the product mixture and form a separate phase, andthus may be easily separated. lf sulfur trioxide has been employed asthe reactant and used in a large excess, the organic materials in theproduct mixture may not form a separate phase. In such an event, thedesired product may be easily recovered by fractional distillation or byextraction with organic solvents. Further purification of the product,if desired, may be accomplished by conventional techniques such asfractional distillation or recrystallization.

The acidic products produced in accordance with the procedures describedabove comprise a major amountof the acid halides. These, of course, maybe converted to the free acids, if desired, by hydrolysis. The acidproducts may then be recovered by extraction with a solvent, such asmethylene chloride. The acids can be converted into their esters byconventional esterification techniques, such as by reaction with analkanol.

If desired, the acidic products obtained by the oxidation reaction maybe converted in situ to acid derivatives such as the esters withoutfirst isolating the acid halide products. For example, the crudeproducts from the oxidation reaction, containing both organic andinorganic phases, may be heated with an alkanol to form the alkylesters. Preferably, a substantial excess of alkanol should be employedin order to insure completeness of the esterification reaction. Afterthe esterification reaction, the organic phase may be separated, waterwashed, dried and then purified by conventional methods such asfractional distillation or recrystallization.

As discussed in copending applications Ser. Nos. 72l,l l7 and 721,115,mentioned supra, the acid halides may be hydrolyzed to the correspondingacid salts with an aqueous base such as potassium hydroxide or sodiumhydroxide. The acid salts exhibit unusually high surface activeproperties and may be used in the manner in which surfactants areconventionally employed such as in the preparation of emulsifiers andsurface coatings and to increase wettability such as in the dyeing oftextile fabrics. From these salts free acids may be generated withaqueous mineral acids such as HCl or H SO The acid halides may also bereacted with an alkanol, as described in more detail in the examples, toform the corresponding esters. The esters are surface active. The estersare particularly useful intermediates for reaction with amines to giveamide derivatives. The amide derivatives are useful as oil, stain andwater repellent agents. The free acids, in addition to being surfaceactive, are useful as oil and stain repellent agents.

The following examples provide a further description of the invention,it being understood that these examples are given for purpose ofillustration only and are not to be regarded as restricting theinvention which is defined by a reasonable interpretation of theappended claims. Parts are by weight except as otherwise indicated.

EXAMPLE I 32.8 G. (0.4l mol) of liquid sulfur trioxide were addeddrop-wise, with stirring, to 25 g. (0.041 mol) of (CF CFO(CF I containedin a 100 ml. 3-neck flask,

equipped with a thermal well, dropping funnel, stirrer and a refluxcondenser, which condenser was connected to a dry ice acetone cooledtrap. The mixture was refluxed for a period of 21 hours and then cooledto 25 C. The flask contents were worked up as follows in order toconvert any acid fluoride product to the corresponding methyl ester. Thecontents of the flask were transferred to a dropping funnel andcarefully added to 64 g. (2.0 mol) of methanol containing 1 ml. ofconcentrated H 50 The resulting mixture was heated under refluxconditions for 18 hours. At the end of this period the mixture wascooled to ambient temperature and allowed to separate into two layers.The lower heavier organic layer weighing 20.7 g. was isolated. Infraredanalysis showed that the lower layer consisted of the iodide startingmaterial. No absorption band consistent with an ester was present. Thefact that no ester was formed established that no acidic products wereformed by the described treatment of (CF CFO(CF l with S0 EXAMPLE [I Theprocedure of Example 1 was repeated with the exception that 2.39 g.(0.004 mol) of antimony pentachloride, SbCl was added to the mixture of(CF CFO(CF I and sulfur trioxide before the first reflux period. Afterthe work-up with the methanol, 20.7 g. of a lower heavier organic layerwere obtained. Infrared analysis indicated that about 41 percent of thislayer consisted of the methyl ester, (CF CFO(CF CO CH (corresponding toa 42 percent conversion). Gas liquid chromatagraphic analysis showed thepresence of about 1 percent of (CF CFO(CF Cl with the balance being theiodide starting material.

EXAMPLE III A mixture of 36.4 g. (0.04 mol) of (CF CFO(CF CF I and 88 g.of 20 percent oleum was charged to apparatus as used in the aboveexamples and refluxed (at about 143 C.) for a period of 18 hours. At theend of this period the reaction mixture was cooled to ambienttemperature and the product mixture was filtered through a sinteredglass filter. The residue collected on the filter was rinsed withconcentrated H 50 and dried on the filter. 36 G. of a solid product wereobtained. The 36 g. of solid product were worked-up as follows in orderto convert any acidic product to the methyl ester. The solid product wasmixed with 50 ml. methanol and 1 ml. of concentrated H SO and heatedunder reflux conditions, with stirring, for a period of two hours. Atthe end of this period the mixture was permitted to cool to 25 C.following which it was filtered to provide 32 g. of a white solid.infrared analysis of the while solid material recovered showed it toconsist mostly of the iodide starting material with a small amount(about 5 percent conversion) of the ester (CF CFO(CF )il z a- EXAMPLE IVThe procedure of Example III was repeated except that 32 g. (0.035 mol)of the starting iodide material (CF CFO(CF CF I and 88 g. of 20 percentoleum were heated under reflux conditions for a period of 96 hoursbefore the work-up with methanol. Infrared analysis of the solid productof this experiment showed that approximately 16 percent of the iodidestarting material was converted to the ester (CF CFO(CF CO C H Thisexperiment shows that increasing the reaction period from l8 hours to 96hours only results in a 16 percent conversion. 5

EXAMPLE V iodide starting material had been converted to the methylester. This experiment shows that the presence of antimony pentachloridehad a significant effect upon the conversion of iodide starting materialto ester product. Approximately twice the conversion was obtained afteronly about half the reaction period used for the experiment of ExampleIV with no catalyst.

EXAMPLES 6 to 34 The procedure of Examples I and III are repeated withS0 and oleum oxidizing agents and with the same molar proportions ofreactants and catalyst except that the iodide starting materials, thecatalysts, and the ester products vary as indicated in the followingtable.

1. The process which comprises reacting a. compounds having the formulawherein R R., are independently selected from the group consisting of F,C1, alkyl and haloalkyl groups in which the halogen atoms are C1 or F, Rand R when taken together and with the carbon chain therebetween, form acyclic structure, R is alkylene or haloalkylene in which the halogenatoms are selected from C1 and F, Y is selected from C1 and F, and Y isselected from H, F, Cl and perhaloalkyl groups in which the halogenatoms are selected from F and Cl, with b. a stoichiometric excess of anoxidizing agent selected from S and oleum, in the presence of anantimony pentahalide selected from SbC1 SbF and SbC 1;,F or mixturesthereof to obtain as the major reaction products the corresponding acidfluorides of the formula R1 F-(B-Ra F-( J-0RCOIl5 F- Ra it.

wherein R R R R and R have the aforestated meanings.

2. The process according to claim 1 which is carried out atsubstantially atmospheric pressure.

3. The process according to claim 1 wherein R -R are selected from F, C1and perhaloalkyl groups.

4. The process according to claim 3 wherein R is a haloalkylene group inwhich the halogen atoms are C1 or F and in which the atomic ratio offluorine atoms to chlorine atoms or to hydrogen atoms or to the combinedtotal of the chlorine and hydrogen atoms in the R group is at least I:l.

5. The process according to claim 4 wherein R R are each F.

6. The process according to claim 5 wherein the R group contains fromone to 40 carbon atoms.

7. The process according to claim 6 wherein the R 8. The processaccording to claim 7 wherein Y and Y are independently selected from thegroup consisting of F and C1 atoms.

9. The process according to claim 8 wherein Y and Y are each F atoms.

10. The process according to claim 9 wherein R is a perhaloalkylenegroup.

11. The process according to claim 9 wherein R has the followingstructure -(CF ),,.(CH ),.--wherein m is an integer of from one to 40and n is O or an integer of from one to 40.

12. The process according to claim 11 wherein m is from one to 15 and nis from zero to 15.

13. The process according to claim 12 wherein the oxidizing agent is $014. The process according to claim 12 which is carried out atsubstantially atmospheric pressure.

15. The process according to claim 12 wherein the oxidizing agent isoleum.

16. The process according to claim 15 which is carried out atsubstantially atmospheric pressure.

17. The process according to claim 1 1 wherein n is 0.

18. The process according to claim 12 wherein n is 0.

19. The process according to claim 18 wherein the oxidizing agent is S0I 20. The process according to claim 19 which is carried out atsubstantially atmospheric pressure.

21. The process according to claim 20 which is carried out in thepresence of SbF 22. The process according to claim 20 which is carriedout in the presence of SbC1 23. The process according to claim 20 inwhich the starting material is (CF CFO(CF CF l.

24. The process according to claim 20 in which the Z S PTlie gi QJS s zz dir iglg wherein the oxidizing agent is oleum.

26. The process according to claim 25 which is carried out atsubstantially atmospheric pressure.

27. The process according to claim 26 which is carried out in thepresence of SbF 28. The process according to claim 26 which is carriedout in the presence of SbCl 29. The process according to claim 26 inwhich the starting material is (CF CFO(CF CF l.

30. The process according to claim 26 in which the starting material is(CF CFO(CF CF I.

2. The process according to claim 1 which is carried out atsubstantially atmospheric pressure.
 3. The process according to claim 1wherein R1-R4 are selected from F, C1 and perhaloalkyl groups.
 4. Theprocess according to claim 3 wherein R is a haloalkylene group in whichthe halogen atoms are C1 or F and in which the atomic ratio of fluorineatoms to chlorine atoms or to hydrogen atoms or to the combined total ofthe chlorine and hydrogen atoms in the R group is at least 1:1.
 5. Theprocess according to claim 4 wherein R1-R4 are each F.
 6. The processaccording to claim 5 wherein the R group contains from one to 40 carbonatoms.
 7. The process according to claim 6 wherein the R group containsfrom one to 15 carbon atoms.
 8. The process according to claim 7 whereinY1 and Y2 are independently selected from the group consisting of F andC1 atoms.
 9. The process according to claim 8 wherein Y1 and Y2 are eachF atoms.
 10. The process according to claim 9 wherein R is aperhaloalkylene group.
 11. The process according to claim 9 wherein Rhas the following structure -(CF2)m(CH2)n-wherein m is an integer offrom one to 40 and n is 0 or an integer of from one to
 40. 12. Theprocess according to claim 11 wherein m is from one to 15 and n is fromzero to
 15. 13. The process according to claim 12 wherein the oxidizingagent is SO3.
 14. The process according to claim 12 which is carried outat substantially atmospheric pressure.
 15. The process according toclaim 12 wherein the oxidizing agent is oleum.
 16. The process accordingto claim 15 which is carried out at substantially atmospheric pressure.17. The process according to claim 11 wherein n is
 0. 18. The processaccording to claim 12 wherein n is
 0. 19. The process according to claim18 wherein the oxidizing agent is SO3.
 20. The process according toclaim 19 which is carried out at substantially atmospheric pressure. 21.The process according to claim 20 which is carried out in the presenceof SbF5.
 22. The process according to claim 20 which is carried out inthe presence of SbC15.
 23. The process according to claim 20 in whichthe starting material is (CF3)2CFO(CF2CF2)3I.
 24. The process accordingto claim 20 in which the starting material is (CF3)2CFO(CF2CF2)6I. 25.The process according to claim 18 wherein the oxidizing agent is oleum.26. The process according to claim 25 which is carried out atsubstantially atmospheric pressure.
 27. The process according to claim26 which is carried out in the presence of SbF5.
 28. The processaccording to claim 26 which is carried out in the presence of SbC15. 29.The process according to claim 26 in which the starting material is(CF3)2CFO(CF2CF2)3I.
 30. The process according to claim 26 in which thestarting material is (CF3)2CFO(CF2CF2)6I.